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You will need a social security number (codice fiscale). It's a personalized tax number used in all commercial dealings. Similar to a Social Security card in the United States or NHS number in UK.

As a resident of Italy, you are allowed to register for national health insurance, called the mutua. You do so through your local USSL or ASL (Azienda Sanitaria Locale) office. Once you are paying the mutua payments, you can visit your assigned doctor, have exams done, and get medications.
Foreigners who get national health insurance have booklets (libretto sanitario) that only last as long as their permesso di soggiorno. When applying, take your passport, residence papers (both permesso di soggiorno and residence certificate), and your codice fiscale and proof of employment (dichiarazione del datore di lavoro), or your marriage certificate.

A separate institution (INAIL covers all workers against the consequences of industrial accidents occurring in the course of employment.